Dyes and Dye Mixtures for Dying Polymers, Method for the Production Thereof and Their Use

Abstract

The present invention relates to dyes of the general formula (1) where R 1 to R 12 and r are each as defined in claim 1 , dye mixtures comprising more than one dye of the general formula (1), their preparation and their use for coloring polymers, particularly polyurethane and polyurethane foam.

1 - 10 . (canceled) 
   
   
       11 . A dye of general formula (1) 
     
       
         
         
             
             
         
       
       wherein 
       R 1  is aryl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl-, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano, wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 13 , wherein R 13  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
       R 2  is hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 14 , wherein R 14  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
       R 3  and R 4  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 15 , wherein R 15  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 5  and R 6  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 16 , wherein R 16  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 7  is hydrogen or (C 1 -C 4 )-alkyl; 
       R 8  is cyano, carbamoyl, or sulfomethyl; 
       R 9 , R 10 , R 11 , and R 12    
       are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; hydroxyl, alkoxy, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, cyano, (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 17 , wherein R 17  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; or wherein two of R 9 , R 10 , R 11 , and R 12  combine with the carbon atoms to which they are attached to define a ring optionally substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; 
       r is 0 or 1, and 
       one or more of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16  and R 17  each contain at least one hydroxyl group. 
     
   
   
       12 . The dye of  claim 11 , wherein
 R 1  is hydroxy-(C 1 -C 4 )-alkyl or hydroxy-(C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkyl;   R 2  is hydrogen, (C 1 -C 4 )-alkyl, hydroxy-(C 1 -C 4 )-alkyl or hydroxy-(C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkyl;   R 3  and R 4  
 are each hydrogen; 
   R 5  and RF
 are, independently, hydrogen; (C 1 -C 4 )-alkyl; hydroxy-(C 1 -C 4 )-alkyl; hydroxy-(C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkyl; (C 1 -C 4 )-alkoxy-(C 1 -C 4 )-alkyl; phenyl; or phenyl substituted by (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy; 
   R 7  is (C 1 -C 4 )-alkyl;   R 8  is cyano; and   R 9  and R 12  
 are, independently, hydrogen, (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy; and r is 0 or 1. 
   
   
   
       13 . The dye of  claim 11 , having the general formula (1a) 
     
       
         
         
             
             
         
       
     
   
   
       14 . The dye of  claim 11 , having the general formula (1c) 
     
       
         
         
             
             
         
       
       wherein 
       R 1  is hydroxyethyl, hydroxypropyl, or hydroxyethoxyethyl; 
       R 2  is methyl, ethyl, hydroxyethyl, hydroxypropyl, or hydroxyethoxyethyl; 
       R 5  and R 6  
 are, independently, hydrogen, (C 1 -C 4 )-alkyl, hydroxyethyl, hydroxypropyl, hydroxy-(C 1 -C 4 )-alkoxyethyl, ethoxy-(C 1 -C 4 )-alkyl, methoxy-(C 1 -C 4 )-alkyl, phenyl, methylphenyl, or methoxyphenyl; and 
 
       R 9  and R 10  
 are, independently, hydrogen, methyl, or methoxy. 
 
     
   
   
       15 . A process for preparing the dye of  claim 11 , comprising diazotizing a compound of general formula (D1) 
     
       
         
         
             
             
         
       
       wherein 
       R 1  is aryl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl-, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano, wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 3 , wherein R 13  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
       R 2  is hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 14 , wherein R 14  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; and 
       R 9 , R 10 , R 11 , and R 12    
       are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; hydroxyl, alkoxy, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, cyano, (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 17 , wherein R 17  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; or wherein two of R 9 , R 10 , R 11 , and R 12  combine with the carbon atoms to which they are attached to define a ring optionally substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; 
       and coupling said compound of general formula (D1) onto a compound of general formula (K1) 
     
     
       
         
         
             
             
         
       
       wherein 
       R 3  and R 4  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 15 , wherein R 15  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 5  and R 6  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 16 , wherein R 16  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 7  is hydrogen or (C 1 -C 4 )-alkyl; and 
       R 8  is cyano, carbamoyl, or sulfomethyl. 
     
   
   
       16 . A process for preparing the dye of  claim 11 , comprising reacting a compound of general formula (ZP1) 
     
       
         
         
             
             
         
       
       wherein 
       R 3  and R 4  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 1 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 15 , wherein R 15  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 5  and R 6  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; or (C 1 -C 60 )-allyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 16 , wherein R 16  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; 
 
       R 7  is hydrogen or (C 1 -C 4 )-alkyl; 
       R 8  is cyano, carbamoyl, or sulfomethyl; 
       R 9 , R 10 , R 11 , and R 12  
 are, independently, hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; hydroxyl, alkoxy, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, cyano, (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 17 , wherein R 17  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; or wherein two of R 9 , R 10 , R 11 , and R 12  combine with the carbon atoms to which they are attached to define a ring optionally substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; and 
 
       r is 0 or 1; 
       with an amine of formula HNR 1 R 2 , wherein 
       R 1  is aryl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano; (C 1 -C 60 )-alkyl substituted by at least one hydroxyl group and optionally substituted by alkoxy, hydroxy-(C 1 -C 40 )-alkyl-, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido, or cyano, wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 13 , wherein R 13  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone; and 
       R 2  is hydrogen; aryl; aryl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-alkylene, halogen, carboxylic ester, carboxamido or cyano; (C 1 -C 60 )-alkyl; (C 1 -C 60 )-alkyl substituted by hydroxyl, alkoxy, hydroxy-(C 1 -C 40 )-alkyl, (C 1 -C 40 )-alkyl, aryl, (C 2 -C 40 )-allylene, halogen, carboxylic ester, carboxamido, or cyano; or (C 1 -C 60 )-alkyl wherein one or more C atoms are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, sulfone, or NR 14 , wherein R 14  is hydrogen, aryl, alkoxy, hydroxyalkyl, or alkyl, wherein one or more C atoms of said alkyl are optionally replaced by oxygen, alkoxylene, arylene, carbonyl, carboxylic ester, carboxamido, or sulfone. 
     
   
   
       17 . A dye mixture comprising two or more dyes of  claim 11 . 
   
   
       18 . A polymer comprising the dye of  claim 11 . 
   
   
       19 . The polymer of  claim 18 , wherein said polymer is polyurethane. 
   
   
       20 . The polymer of  claim 18 , wherein said polymer is polyurethane foam. 
   
   
       21 . A polymer comprising the dye mixture of  claim 17 . 
   
   
       22 . The polymer of  claim 21 , wherein said polymer is polyurethane. 
   
   
       23 . The polymer of  claim 21 , wherein said polymer is polyurethane foam.